CN101735433A - Poly(alkene carbonate) diol-poly(lactic acid) block copolymer and preparation method thereof - Google Patents
Poly(alkene carbonate) diol-poly(lactic acid) block copolymer and preparation method thereof Download PDFInfo
- Publication number
- CN101735433A CN101735433A CN200910155893A CN200910155893A CN101735433A CN 101735433 A CN101735433 A CN 101735433A CN 200910155893 A CN200910155893 A CN 200910155893A CN 200910155893 A CN200910155893 A CN 200910155893A CN 101735433 A CN101735433 A CN 101735433A
- Authority
- CN
- China
- Prior art keywords
- poly
- carbonate
- molecular weight
- diol
- block copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Images
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a poly(alkene carbonate) diol-poly(lactic acid) block copolymer and a preparation method thereof. A copolyester of the invention is a block copolymer formed by ring-opening copolymerization of poly (alkene carbonate) diol with the weight average molecular weight of between 500 and 1,000g/mol and lactide. The concrete preparation method comprises the steps of: performing vacuum pumping-nitrogen charge permutation operation on a reactant which is fully dried in advance, the lactide and a ring-opening catalyst in a container for 5 to 10 times; and finally, pumping high vacuum to be between 5 and 15Pa, and increasing the temperature to be between 110 and 180 DEG C to react for 6 to 72 hours to finally obtain the poly(alkene carbonate) diol-poly(lactic acid) block copolymer with high molecular weight, wherein the reactant is one or more of poly(ethylene carbonate) diol, poly(propylene carbonate) diol and poly(butylene carbonate) diol. The method simplifies process operation, and can adjust the chain segment length of a final product and the molecular weight of the copolymer by controlling the molecular weight and the adding amount of the poly(alkene carbonate) diol to obtain copolyesters with different performances.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of polymerized thylene carbonate esterdiol-polylactic-acid block copolymer, the invention still further relates to the preparation method of this copolyesters.
Background technology
The polymerized thylene carbonate diol ester is a kind of macromolecular material that utilizes carbonic acid gas and synthesis of epoxy compounds to form, wherein aliphatics polymerized thylene carbonate diol ester has good biodegradability, and this kind polyester generally has good low-temperature kindliness, barrier properties for gases and transparency, makes carrier, film packing material, solid electrolyte, inorganic filler surface processing of its useful as drug slow-releasing system etc.But because the relatively poor thermostability of aliphatics polymerized thylene carbonate diol ester self has a strong impact on its practical application in every field.
In the research of aliphatics polymerized thylene carbonate diol ester, studying morely both at home and abroad has polymerized thylene carbonate glycol ester glycol, polymerized thylene carbonate butanediol ester glycol, the copolymerization of polymerized thylene carbonate propylene glycol ester glycol and other compounds, such as synthesizing polymerized thylene carbonate urethane elastomer (CN1865311A) by polymerized thylene carbonate ethyl ester and vulcabond, be the polycarbonate type books elastomerics (Xie Xingyi that the synthetic class of raw material has premium properties for example again with poly-own diamyl two carbonic ether dibasic alcohol, Liu is anti-, the clock elecscreen. the biomedical engineering magazine, 1999,16:121-122), perhaps synthesize some solvent-proof aliphatic polycarbonate type polyurethane elastomerics (Harris RF, Joseph MD, Avisdson CD er al.J Appl Polym Sci, 1990,41:487-507), perhaps with poly (propylene carbonate) and tolylene diisocyanate be raw material synthesized the poly (propylene carbonate) polyurethane elastomer (Peng Han etc. the synthetic and performance of poly (propylene carbonate) polyurethane elastomer, chemistry world, 1995,8:426-428).
Poly(lactic acid) is the present awfully hot a kind of degradable material of research, and it is to be a kind of environment-friendly material that the basic raw material vegetation obtains with the lactic acid that amylofermentation obtains, and it not only has good physicals, also has a biodegradability.But the too high meeting of local lactic acid concn causes inflammation in the degradation process of PLLA in the body temperature environment; Simultaneously, PLLA has higher degree of crystallinity, so the degradation cycle of PLLA is long, these have all limited its range of application at medical field.
In sum, utilize the macromolecular material of these two kinds of different performances of polymerized thylene carbonate ethyl ester compound and poly(lactic acid) to carry out copolymerization, poly propylene carbonate-poly(lactic acid) copolyester material with development of new is learnt from other's strong points to offset one's weaknesses it on performance, performance advantage separately is very significant to greatest extent.
Summary of the invention
The objective of the invention is provides a kind of copolyesters with biological degradation potential quality at the above-mentioned state of the art, and this copolyesters is synthetic easily, the molecular weight height, and the present invention simultaneously also provides a kind of technology copolyesters preparation method simple, with low cost.
Copolyesters of the present invention is that poly propylene carbonate dibasic alcohol molecule and the rac-Lactide ring opening copolymer of 1000～10000g/mol forms by weight-average molecular weight, and the copolyesters of gained is a segmented copolymer.Wherein:
The molecular formula of described poly propylene carbonate dibasic alcohol molecule is
Radicals R is
In one or more.
The method that the present invention adopts the poly propylene carbonate dibasic alcohol to cause the rac-Lactide ring-opening polymerization prepares above-mentioned copolyesters, and concrete grammar is as follows:
The reactant of thorough drying in advance and rac-Lactide and ring opening catalyst are put into container, then container is vacuumized, fill nitrogen again, vacuumize-fill the nitrogen replacement operator 5～10 times, last pumping high vacuum to 5～15Pa and sealed vessel, be warming up to 110～180 ℃, reacted 6～72 hours, obtain high-molecular weight polymerized thylene carbonate esterdiol-polylactic-acid block copolymer at last.
Described reactant is that weight-average molecular weight is one or more in the polymerized thylene carbonate ethyl ester glycol, poly (propylene carbonate) glycol, polymerized thylene carbonate butyl ester glycol of 1000～10000g/mol; The reactant that adds and the mass ratio of rac-Lactide are 1: 0.001～1000.
Described ring opening catalyst is one or more in stannous octoate, Dibutyltin oxide, tributyltin oxide and the tin protochloride; The add-on of ring opening catalyst is 0.001～20% of reactant and a rac-Lactide quality summation.
The invention has the advantages that: the inventive method has been simplified technological operation, can be by the molecular weight of control polymerized thylene carbonate esterdiol and the chain length and the molecular weight of copolymer of add-on adjusting final product, the copolyesters that obtained performance is different.
Description of drawings
Fig. 1 is the nuclear magnetic spectrogram of the copolyesters of the present invention's acquisition.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
With the 0.1g molecular weight of thorough drying in advance is that polymerized thylene carbonate ethyl ester glycol, 100g rac-Lactide and the 0.01g stannous octoate of 1000g/mol put into the 250ml narrow-mouthed bottle, be evacuated to and be lower than 30Pa, charge into the exsiccant high pure nitrogen, then repeat to vacuumize-fill the nitrogen operation more than 5 times, be evacuated to 10Pa at last, the sealed reaction bottle is warming up to 180 ℃, reacted 6 hours, obtaining molecular weight at last is that 86Kg/mol, molecular weight distribution are polymerized thylene carbonate ethyl ester glycol-polylactic-acid block copolymer of 1.99.
With the 20.0g molecular weight of thorough drying in advance is that the polymerized thylene carbonate ethyl ester glycol of 1200g/mol, poly (propylene carbonate) glycol, 100.0g rac-Lactide and 0.015g and the Dibutyltin oxide that the 30.0g molecular weight is 500g/mol are put into the 250ml narrow-mouthed bottle, be evacuated to and be lower than 30Pa, charge into the exsiccant high pure nitrogen, then repeat to vacuumize-fill nitrogen operation 5 times, be evacuated to 12Pa at last, the sealed reaction bottle, be warming up to 160 ℃, reacted 12 hours, obtaining molecular weight at last is that 58Kg/mol, molecular weight distribution are polymerized thylene carbonate esterdiol-polylactic-acid block copolymer of 1.71.
With the 30.0g molecular weight of thorough drying in advance is the polymerized thylene carbonate ethyl ester glycol of 2000g/mol, 30.0g molecular weight is the poly (propylene carbonate) glycol of 1500g/mol, 40.0g molecular weight is the polymerized thylene carbonate butyl ester glycol of 2000g/mol, 100g rac-Lactide and 0.001g and Dibutyltin oxide, 0.001g tributyltin oxide is put into the 250ml narrow-mouthed bottle, be evacuated to and be lower than 30Pa, charge into the exsiccant high pure nitrogen, then repeat to vacuumize-fill nitrogen operation 6 times, be evacuated to 5Pa at last, the sealed reaction bottle, be warming up to 150 ℃, reacted 16 hours, obtaining molecular weight at last is 66Kg/mol, molecular weight distribution is polymerized thylene carbonate esterdiol-polylactic-acid block copolymer of 1.53.The nuclear-magnetism spectrum of the copolyesters that obtains as shown in Figure 1.
With the 100.0g molecular weight of thorough drying in advance is that polymerized thylene carbonate butyl ester glycol, 1.15g rac-Lactide and 0.36g Dibutyltin oxide, 0.05g tributyltin oxide, the 0.25g tin protochloride of 5000g/mol put into the 250ml narrow-mouthed bottle, be evacuated to and be lower than 30Pa, charge into the exsiccant high pure nitrogen, then repeat to vacuumize-fill nitrogen operation 8 times, be evacuated to 5Pa at last, the sealed reaction bottle, be warming up to 140 ℃, reacted 24 hours, obtaining molecular weight at last is that 67Kg/mol, molecular weight distribution are polymerized thylene carbonate butyl ester glycol-polylactic-acid block copolymer of 2.15.
With the 100.0g molecular weight of thorough drying in advance is that polymerized thylene carbonate ethyl ester glycol, 13g rac-Lactide and the 0.054g tributyltin oxide of 1000g/mol put into the 250ml narrow-mouthed bottle, be evacuated to and be lower than 30Pa, charge into the exsiccant high pure nitrogen, then repeat to vacuumize-fill nitrogen operation 8 times, be evacuated to 15Pa at last, the sealed reaction bottle is warming up to 130 ℃, reacted 48 hours, obtaining molecular weight at last is that 72Kg/mol, molecular weight distribution are polymerized thylene carbonate ethyl ester glycol-polylactic-acid block copolymer of 1.59.
With the 100g molecular weight of thorough drying in advance is that poly (propylene carbonate) glycol, 0.1g rac-Lactide and the 10g tin protochloride of 1500g/mol put into the 250ml narrow-mouthed bottle, be evacuated to and be lower than 30Pa, charge into the exsiccant high pure nitrogen, then repeat to vacuumize-fill nitrogen operation 10 times, be evacuated to 5Pa at last, the sealed reaction bottle is warming up to 120 ℃, reacted 64 hours, obtaining molecular weight at last is that 72Kg/mol, molecular weight distribution are poly (propylene carbonate) glycol-polylactic-acid block copolymer of 1.93.
With the 0.1g molecular weight of thorough drying in advance is that poly (propylene carbonate) glycol, 99.9g rac-Lactide and the 20g Dibutyltin oxide of 10000g/mol put into the 250ml narrow-mouthed bottle, be evacuated to and be lower than 30Pa, charge into the exsiccant high pure nitrogen, then repeat to vacuumize-fill nitrogen operation 10 times, be evacuated to 15Pa at last, the sealed reaction bottle is warming up to 110 ℃, reacted 72 hours, obtaining molecular weight at last is that 51Kg/mol, molecular weight distribution are poly (propylene carbonate) glycol-polylactic-acid block copolymer of 1.86.
Claims (3)
1. polymerized thylene carbonate esterdiol-polylactic-acid block copolymer is characterized in that: this copolyesters is that poly propylene carbonate dibasic alcohol molecule and the rac-Lactide ring opening copolymer of 1000～10000g/mol forms by weight-average molecular weight, is segmented copolymer, wherein:
The molecular formula of described poly propylene carbonate dibasic alcohol molecule is
Radicals R is
In one or more.
2. the method for preparing polymerized thylene carbonate esterdiol-polylactic-acid block copolymer, it is characterized in that this method adopts the poly propylene carbonate dibasic alcohol to cause the method for rac-Lactide ring-opening polymerization, specifically: the reactant of thorough drying and rac-Lactide and ring opening catalyst are put into container in advance, then container is vacuumized, fill nitrogen again, vacuumize-fill the nitrogen replacement operator 5～10 times, last pumping high vacuum to 5～15Pa and sealed vessel, be warming up to 110～180 ℃, reacted 6～72 hours, and obtained high-molecular weight polymerized thylene carbonate esterdiol-polylactic-acid block copolymer at last;
Described reactant is that weight-average molecular weight is one or more in the polymerized thylene carbonate ethyl ester glycol, poly (propylene carbonate) glycol, polymerized thylene carbonate butyl ester glycol of 1000～10000g/mol; The reactant that adds and the mass ratio of rac-Lactide are 1: 0.001～1000.
3. the method for preparing polymerized thylene carbonate esterdiol-polylactic-acid block copolymer as claimed in claim 2 is characterized in that: described ring opening catalyst is one or more in stannous octoate, Dibutyltin oxide, tributyltin oxide and the tin protochloride; The add-on of ring opening catalyst is 0.001～20% of reactant and a rac-Lactide quality summation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910155893A CN101735433A (en) | 2009-12-29 | 2009-12-29 | Poly(alkene carbonate) diol-poly(lactic acid) block copolymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910155893A CN101735433A (en) | 2009-12-29 | 2009-12-29 | Poly(alkene carbonate) diol-poly(lactic acid) block copolymer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101735433A true CN101735433A (en) | 2010-06-16 |
Family
ID=42459502
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910155893A Withdrawn CN101735433A (en) | 2009-12-29 | 2009-12-29 | Poly(alkene carbonate) diol-poly(lactic acid) block copolymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101735433A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002142A (en) * | 2010-09-21 | 2011-04-06 | 中国科学院宁波材料技术与工程研究所 | Biodegradable polyurethane and preparation method thereof |
| CN102241813A (en) * | 2010-05-10 | 2011-11-16 | 江苏中科金龙化工股份有限公司 | Poly (alkene carbonate) diol-polylactic acid segmented copolymer and preparation method thereof |
| CN104080832A (en) * | 2011-09-08 | 2014-10-01 | 英佩雷尔创新有限公司 | Method of synthesizing polycarbonate in presence of bimetallic catalyst and chain transfer agent |
| CN104212166A (en) * | 2014-09-05 | 2014-12-17 | 东莞市瀛通电线有限公司 | Degradable material for signal line and preparation method of degradable material |
| CN108909114A (en) * | 2018-06-14 | 2018-11-30 | 深圳市通产丽星股份有限公司 | A kind of carbon dioxide-base composite material and preparation method |
-
2009
- 2009-12-29 CN CN200910155893A patent/CN101735433A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241813A (en) * | 2010-05-10 | 2011-11-16 | 江苏中科金龙化工股份有限公司 | Poly (alkene carbonate) diol-polylactic acid segmented copolymer and preparation method thereof |
| CN102002142A (en) * | 2010-09-21 | 2011-04-06 | 中国科学院宁波材料技术与工程研究所 | Biodegradable polyurethane and preparation method thereof |
| CN104080832A (en) * | 2011-09-08 | 2014-10-01 | 英佩雷尔创新有限公司 | Method of synthesizing polycarbonate in presence of bimetallic catalyst and chain transfer agent |
| CN108707225A (en) * | 2011-09-08 | 2018-10-26 | 英佩雷尔创新有限公司 | The method of polycarbonate synthesis in the presence of bimetallic catalyst and chain-transferring agent |
| CN104212166A (en) * | 2014-09-05 | 2014-12-17 | 东莞市瀛通电线有限公司 | Degradable material for signal line and preparation method of degradable material |
| CN108909114A (en) * | 2018-06-14 | 2018-11-30 | 深圳市通产丽星股份有限公司 | A kind of carbon dioxide-base composite material and preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tang et al. | Metal‐free synthesis of novel biobased dihydroxyl‐terminated aliphatic polyesters as building blocks for thermoplastic polyurethanes | |
| CN108250415B (en) | Poly (gamma-butyrolactone) -b-polylactic acid block copolymer and preparation method thereof | |
| CN100558787C (en) | A kind of preparation method of full biodegradation polyester copolymer | |
| CN101735433A (en) | Poly(alkene carbonate) diol-poly(lactic acid) block copolymer and preparation method thereof | |
| CN100523050C (en) | Method for preparing polylactic acid-polycarbonate copolymers | |
| Ye et al. | Nonisocyanate CO2-based poly (ester-co-urethane) s with tunable performances: A potential alternative to improve the biodegradability of PBAT | |
| Luo et al. | Synthesis of aliphatic carbonate macrodiols and their application as sustainable feedstock for polyurethane | |
| Danko et al. | Ring-opening polymerization of γ-butyrolactone and its derivatives: a review | |
| Huang et al. | Cross-linked networks in poly (propylene carbonate) by incorporating (maleic anhydride/cis-1, 2, 3, 6-tetrahydrophthalic anhydride) oligomer in CO2/propylene oxide copolymerization: improving and tailoring thermal, mechanical, and dimensional properties | |
| CN102241813A (en) | Poly (alkene carbonate) diol-polylactic acid segmented copolymer and preparation method thereof | |
| CN109575257B (en) | Poly (2, 5-furandicarboxylic acid-1, 4-butanedioic acid neopentyl glycol ester), and preparation method and product thereof | |
| Chaber et al. | The heterogeneous selective reduction of PHB as a useful method for preparation of oligodiols and surface modification | |
| Lorenzini et al. | High glass transition temperature bio-based copolyesters from poly (3-hydroxybutyrate-co-3-hydroxyvalerate) and isosorbide | |
| KR101318734B1 (en) | Triblock copolymers between polyalkylene carbonate and polylactide and method for producing the same | |
| CN101735434A (en) | Poly(alkene carbonate) diol-polybutylene succinate copolymer and preparation method thereof | |
| Zhao et al. | Preparation of degradable polymenthide and its elastomers from biobased menthide via organocatalyzed ring-opening polymerization and UV curing | |
| CN105273185A (en) | Method for preparing aliphatic-aromatic mixed block thermoplastic polyurethane through nonisocyanate method | |
| CN115322350B (en) | Degradable bio-based polyester and preparation method and application thereof | |
| CN102241814A (en) | Poly(alkene carbonate)diol-poly(butylene succinate) copolymer and preparation method thereof | |
| CN114316287B (en) | Preparation method of lignin-containing polyester polyol | |
| Zeng et al. | A new approach to prepare high molecular weight poly (p-dioxanone) by chain-extending from dihydroxyl terminated propolymers | |
| CN115403748A (en) | Polycaprolactone derivative and preparation method thereof | |
| US8633294B2 (en) | Lactic acid-isosorbide copolyesters and process for the preparation thereof | |
| EP3992226B1 (en) | Method for preparing block copolymer | |
| Zhang et al. | Ring-opening copolymerization of hydroxyproline-derived thiolactones and lipoic acid derivatives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C04 | Withdrawal of patent application after publication (patent law 2001) | ||
| WW01 | Invention patent application withdrawn after publication |
Open date: 20100616 |